Silicon nitride sintered product

ABSTRACT

A silicon nitride sintered product comprises, in % by weight, 1 to 10% Mg, calculated as MgO, 1 to 10% Zr, calculated as ZrO 2 , 0.1 to 2.0% of at least one of Al, calculated as Al 2  O 3 , Li, calculated as Li 2  O, and Na, calculated as Na 2  O, and the remainder being Si 3  N 4  and unavoidable impurities.

FIELD OF THE INVENTION

This invention relates to silicon nitride sintered product, particularly to silicon nitride sintered product improved in resistance against chipping and wear.

The silicon nitride sintered product of this invention is suitably used for wear resistant industrial members such as cutting tools and the like.

BACKGROUND OF THE INVENTION

Known additive components suitably employed for cutting tools are MgO and ZrO₂ as disclosed in JP-B-60-16388 and 60-20346 (the term "JP-B" as used herein means an "examined Japanese patent publication"). Al₂ O₃, WC, Y₂ O₃, etc., are also disclosed in JP-A-56-73670 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"). Further, though not being limited to cutting tools, addition of magnesia-alumina spinel and partially stabilized ZrO₂ is disclosed in JP-A-60-77174 to improve mechanical properties.

The above-mentioned conventional techniques are useful for improving strength and toughness; in addition to such improvements, however, further reduction of wear is required to prolong a tool life.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a silicon nitride sintered product improved in resistances against chipping and wear to meet the above requirements.

According to the present invention, there is provided a silicon nitride sintered product comprising by weight,

1 to 10% Mg (calculated as MgO),

1 to 10% Zr (calculated as ZrO₂),

0.1 to 2.0% at least one of Al (calculated as Al₂ O₃), Li (calculated as Li₂ O) and Na (calculated as Na₂ O) and

the remainder being Si₃ N₄ and unavoidable impurities.

DETAILED DESCRIPTION OF THE INVENTION

Components Mg, Zr, Al, Li and Na contribute to product densification by forming liquid phase in the interstices between Si₃ N₄ particles together with Si, N and O during the firing, and also bond Si₃ N₄ particles by glassification during cooling. Especially, Al, Li and Na enhance bonding strength of Si₃ N₄ particles in the intergrannular phase and avoid debonding of Si₃ N₄ particles during abrasion. When the bonding strength is appropriate, the so-called "pull-out", i.e., a pulling out phenomenon of Si₃ N₄ columnar crystal, occurs, so that stress concentration at the tip of the crack is considerably reduced to give high toughness to the sintered product. In this respect Al is the most effective among Al, Ni and Na. Al reinforces bonding of Si₃ N₄ particles, and avoids debonding of Si₃ N₄ particles during abrasion. A part of the Zr is often incorporated as represented by ZrO_(x) N_(y) C_(z) in the sintered product.

The reason for limiting the respective contents of Mg and Zr as 1 to 10% by weight each (calculated as MgO and ZrO₂, respectively) is given below. When the amount is less than 1%, no densification is attained, whereas an amount exceeding 10% leads to an excess formation of intergranular phase that neither high toughness nor high strength is achieved. The amount of at least one of Al, Li and Na is limited to 0.1 to 2.0% by weight in oxide base, since when the addition is lower than said limit, debonding of Si₃ N₄ particles occurs during abrasion due to insufficient adhesion strength between the Si₃ N₄ particles, leading the deterioration of wear resistance. When an addition exceeds 2.0%, on the other hand, the bonding strength of the Si₃ N₄ particles in the intergranular phase becomes too strong, thereby depressing the "pullout" phenomenon and avoiding toughening thereof.

The sintered product of the present invention can be obtained, for instance, by firing a mixture of Mg compounds, Zr compounds, and compounds of at least one of Al, Li, and Na, which may give oxides when each is solely fired, wherein the mixture comprises, in an oxide base, by weight, 1 to 10% Mg, 1 to 10% Zr, and 0.1 to 2.0% of at least one of Al, Li, and Na, and Si₃ N₄ powder as the remainder. The mixture is molded and fired at 1,500 to 1,900° C. under nitrogen or an inert gas atmosphere. Preferable is gas pressure sintering, but is not limited thereto.

The gas-pressure sintering is carried out under overpressure of N₂ gas, typically in the range of 2 to 300 atoms, more preferably 5 to 100 atoms. Since the over-pressure of N₂ gas suppresses decomposition of Si₃ N₄ at high temperature, in the gas-pressure sintering higher sintering temperature can be employed to form fully dense sintered products.

As is clear from the above explanations, the silicon nitride sintered product of the present invention enables longer cutting tool life, maintaining the mechanical strength comparable to the conventional silicon nitride sintered products.

The present invention is hereinafter described in greater detail with reference to examples, which are not to be construed as limiting the scope thereof. Unless otherwise indicated, all parts, percents, and ratios are by weight.

EXAMPLES 1-5 AND COMPARATIVE EXAMPLES 6-9

Si₃ N₄ powder having average particle size (diameter) or 0.7 μm and BET specific surface area of 10 m² /g, MgCO₃ powder having 20 m³ /g, ZrO₂ powder having 10 m² /g, and Al₂ O₃ powder having 10 m² /g were weighted out, as shown in Table 1, subjected to wet mixing for 16 hours using a pot mill with balls made of Si₃ N₄, dried, and granulated to an average diameter of 250 μm. The powder granules were molded in a metal mold under a pressure of 1.5 ton/cm², and fired under conditions as shown in Table 1 to give silicon nitride sintered products of Nos. 1 to 9.

Flexural strength at room temperature according to Japanese Industrial Standard (JIS R1601), fracture toughness by IM method, and resistances against wear and chipping were measured on the sintered products of No. 1 to No. 9 and the results are shown in Table 1.

Regarding cutting property in Table 1, a wear resistance is shown as a flank wear width V_(B), which was measured by using test piece formed by the method specified in JIS B4103, SNGN 432 with chamfer on 0.05 to machine a cutting material (JIS FC23) in 240 dia.×200 length, conditions such as cutting speed of 180 m/min, depth of cut of 1.0 mm, feed of 0.15 mm/rev. and cutting length of 800 mm. A chipping resistance is shown as number of disks which were successfully cut without chipping, using a test piece formed by the method specified in JIS B4103, SNGN432 with chamfer of 0.05 to machine a cutting material JIS FC23 having black skin, outer flank of the disk with an 11 mm thickness and an outer diameter of 200 mm in an axial direction under conditions of a cutting speed of 150 m/min, feed of 0.3 m/rev. and depth of cut of 2.0 mm.

                                      TABLE 1                                      __________________________________________________________________________                                            Machining                                                          Mechanical  Properties                                     Sintering Aid                                                                           Al.sub.2 O.sub.3                                                                          Properties  Wear Chip                                      MgCO.sub.3                                                                              Addi-      Flexural    Resist-                                                                             ping                                      (as MgO)                                                                            ZrO.sub.2                                                                          tion                                                                               Firing Strength                                                                             Toughness                                                                            ance Resist-                            Sample No.                                                                            (%)  (%) (%) Condition                                                                             (kg/mm.sup.2)                                                                        (MN/m.sup.3/2)                                                                       (V.sub.B mm)                                                                        ance                                                                               Remarks                        __________________________________________________________________________     Example 1                                                                             5    5   0.2 1800° C./2H                                                                    100   8.0   0.15 >200                               Example 2                                                                             "    5 0.5                                                                              "   95     8.0   0.15  >200                                    Example 3                                                                             "    5 0.7                                                                              1800° C./2H                                                                 95     7.5   0.17  164                                                     N.sub.2 10 atm                                                 Example 4                                                                             3    7 1.5                                                                              "   88     6.3   0.17  143                                     Example 5                                                                             5    10 0.5                                                                             "   85     7.4   0.18  175                                     Comparative                                                                           5    5 0 1800° C./2H                                                                 102    8.2   0.45  >200 High Wear                          Example 6       N.sub.2 80 atm                                                 Comparative                                                                           "    5   3.0 1800° C./2H                                                                    90    5.2   0.30 10  Consider-                      Example 7           N.sub.2 10 atm              able                                                                           chipping                       Comparative                                                                           0    7 1.0                                                                              1800° C./2H                                                                 77     4.8   0.32  8    "                                  Example 8       N.sub.2 80 atm                                                 Comparative                                                                           5    0 1.0                                                                              "   80     5.5   0.31  10   "                                  Example 9                                                                      __________________________________________________________________________

As is seen in Table 1, it is considered that sintered test piece No. 6 gave high wear due to Al₂ O₃ deficiency, No. 7 showed poor toughness due to excess Al₂ O₃, and test pieces No. 8 and No. 9 were not dense enough, due to the deficiency of Mg and Zr respectively, and were poor in overall properties.

EXAMPLES 10-14 AND COMPARATIVE EXAMPLES 16-17

Li₂ CO₃ powder having a specific surface area of 8 m² /g and Na₂ CO₃ powder having 10 m² /g were additionally used, and the powder mixtures, in the ratio shown in Table 2, were processed according to the same process as in Example 3 to give sintered products No. 10 to No. 17. The properties are measured and the results are shown in Table 2.

                                      TABLE 2                                      __________________________________________________________________________                                    Mechanical                                             Sintering Aid Li.sub.2 CO.sub.3                                                                   Na.sub.2 CO.sub.3                                                                   Properties  Machining Properties                       MgCO.sub.3                                                                               Al.sub.2 O.sub.3                                                                   Addition                                                                            Addition                                                                             Flexural   Wear                                       (as MGO)                                                                            ZrO.sub.2                                                                          Addition                                                                            (as Li.sub.2 O)                                                                     (as Na.sub.2 O)                                                                     Strength                                                                             Toughness                                                                            Resistance                                                                           Chipping                      Sample No.                                                                            (%)  (%) (%)  (%)  (%)  (kg/mm.sup.2)                                                                        (MN/m.sup.3/2)                                                                       (V.sub.B mm)                                                                         Resistance                    __________________________________________________________________________     Example 10                                                                            5    5   --   1.0  --   85    6.1   0.22  123                           Example 11                                                                            5    5   --   --   1.0  83    6.0   0.20  150                           Example 12                                                                            3    7   0.8  --   0.5  91    6.5   0.18  166                           Example 13                                                                            3    7   0.7  0.3  --   90    7.0   0.17  >200                          Example 14                                                                            5    5   0.5  0.5  0.5  88    6.6   0.18  152                           Comparative                                                                           5    5   --   3.0  --   78    5.0   0.36  8                             Example 15                                                                     Comparative                                                                           5    5   --   --   3.0  81    4.9   0.39  8                             Example 16                                                                     Comparative                                                                           5    5   1.5  1.0  1.0  75    4.9   0.36  10                            Example 17                                                                     __________________________________________________________________________

As is seen in Table 2, both Li and Na had the same effect as Al on the sintered products.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. 

What is claimed is:
 1. A silicon nitride sintered product consisting essentially of, in % by weight:1 to 10% Mg, calculated as MgO; 1 to 10% Zr, calculated as ZrO₂ ; 0.1 to 2.0% of at least one of Al, calculated as Al₂ O₃, Li, calculated as Li₂ O, and Na, calculated as Na₂ O; and the remainder being Si₃ N₄ and unavoidable impurities.
 2. A silicon nitride sintered product as in claim 1 consisting essentially of MgO, ZrO₂ and Al₂ O₃ in the amounts specified, the remainder being Si₃ N₄. 